Vinylsulfone derivative, liquid crystal composition comprising the same and compensation film using the same liquid crystal composition

ABSTRACT

Disclosed are a vinylsulfone derivative, a liquid crystal composition comprising the same, and a compensation film for a liquid crystal display device using the same liquid crystal composition. More particularly, the vinylsulfone derivative is a liquid crystal material of a high-quality view angle compensation film, which improves a contrast ratio measured at a tilt angle when compared to a contrast ratio measured from the front surface and minimizes color variations in a black state depending on view angles.

This application claims the benefit of the filing date of Korean PatentApplication No. 10-2005-0112316, filed on Nov. 23, 2005, in the KoreanIntellectual Property Office, the disclosure of which is incorporatedherein in its entirety by reference.

BACKGROUND OF THE INVENTION

(a) Field of the Invention

The present invention relates to a vinylsulfone derivative, a liquidcrystal composition comprising the same, and a compensation film for aliquid crystal display device using the same liquid crystal composition.More particularly, the present invention relates to a liquid crystalmaterial of a high-quality view angle compensation film, which improvesa contrast ratio measured at a tilt angle when compared to a contrastratio measured from the front surface and minimizes color variations ina black state depending on view angles. The present invention alsorelates to a liquid crystal composition comprising the same liquidcrystal material and a compensation film obtained from the same liquidcrystal composition.

(b) Description of the Related Art

Recently, as watches, notebook PCs, cellular phones, televisions andmonitors have extended the market, display devices having low weight andrequiring low power consumption have been increasingly in demand. Sinceliquid crystal display devices (LCDs) are light and thin and require lowpower consumption, they have been widely applied to such products.

However, a liquid crystal display device has a disadvantage of viewangle dependency. In other words, an LCD shows variations in color orlight/darkness depending on view directions or angles. Additionally, asthe screen of an LCD increases in size, view angle decreases more andmore. As compared to a conventional CRT (cathode ray tube) device havinga view angle of about 180°, a TFT-LCD with no view angle compensationshows a view angle of merely about ±50°.

To solve the above problem, various methods have been used, such methodsincluding a multi-domain method in which pixels are divided in liquidcrystal cells to control the liquid crystal alignment, a method ofcontrolling a voltage and a method of utilizing an optical compensationfilm.

The above-mentioned view angle dependency of a liquid crystal displaydevices is caused by the incident light having a tilt angle to the LCDpanel, which shows a birefringence effect different from that of thevertical incident light. To compensate for this, an optical compensationfilm has been widely used. Herein, retardation films having an oppositebirefringence index to the panel are attached onto both surfaces of thepanel. Also, as display panels have increased in size, there has been aneed for a high-quality liquid crystal compensation film.

A retardation film is obtained by coating an aligned transparent supportwith liquid crystal, and aligning the liquid crystal along apredetermined direction to the direction of an aligning layer, followedby curing. After aligning, the liquid crystal has a direction oppositeto the direction of liquid crystal cells upon application of a voltage,so that light leakage in a black state can be minimized. When combiningsuch retardation films with a liquid crystal panel and light is allowedto penetrate through the panel, it is possible to compensate for aretardation of light caused by a difference of light paths, because theincident light has a similar path in all directions. Additionally, it isalso possible to perform compensation of a difference in birefringenceindexes in all directions by optimizing a birefringence latitude of eachfilm, an angle formed between films, a rubbing direction and an angle toa polarizer.

A liquid crystal compound used to manufacture such films should bestable against moisture, light, heat, air, electric fields, or the like.Also, the liquid crystal compound should be chemically stable under anenvironment of use. Further, in order to apply a liquid crystal compoundto a display device, the compound should have adequately balancedphysical properties, including a broad range of liquid crystal phasetemperatures and refraction anisotropy (Δn). Under these circumstances,there is a need for a novel liquid crystal compound satisfying variousphysical properties required for various types of display devices.

SUMMARY OF THE INVENTION

Therefore, the present invention has been made in view of theabove-mentioned problems. It is an object of the present invention toprovide a novel vinylsulfone derivative useful as a material for a viewangle compensation film that can improve a contrast ratio and minimizevariations in color depending on view angles in a black state.

It is another object of the present invention to provide a liquidcrystal composition comprising the above vinylsulfone derivative, and acompensation film for liquid crystal display device using the aboveliquid crystal composition.

According to an aspect of the present invention, there is provided anovel vinylsulfone derivative. Also, the present invention provides aliquid crystal composition comprising the above vinylsulfone derivative,and a compensation film for liquid crystal display device using thesame.

BRIEF DESCRIPTION OF THE DRAWINGS

The foregoing and other objects, features and advantages of the presentinvention will become more apparent from the following detaileddescription when taken in conjunction with the accompanying drawings inwhich:

FIG. 1 is a photographic view taken by a polarizing microscope, whichshows a liquid crystal display using a compensation film according to apreferred embodiment of the present invention in a black state; and

FIG. 2 is a photographic view taken by a polarizing microscope, whichshows a nematic liquid crystal phase of the liquid crystal compositionaccording to a preferred embodiment of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

Hereinafter, the present invention will be explained in more detail.

The novel vinylsulfone derivative according to the present invention isrepresented by the following Formula 1:

wherein X¹ is —O—, —NH—, —CH₂CH₂O—, —CH₂CH₂NH— or —(CH₂)_(m)—, and m is1 or 2;

A¹ is a C₁˜C₁₂ alkylene, a C₂˜C₁₂ alkenylene, —(CH₂CH₂O)_(n)—,—(CH₂CHCH₃O)_(n)— or —(CHCH₃CH₂O)_(n)—, and n is an integer of 1˜5;

each of Y¹ and Y² independently represents —O—, —NH—, —(CH₂)_(p)—,—CH═CH—, —C≡C—, —C(═O)O—, —OC(═O)— or —C(═O)—, and p is an integer of0˜2;

a is an integer of 0˜2;

each of Q¹˜Q⁴, R¹˜R⁴ and R⁶˜R⁹ independently represents —H, —F, —Cl,—Br, —I, —CN, —OH, —CH₃, —CH₂CH₃ or —C(═O)CH₃; and

R⁵ is —H, —F, —Cl, —Br, —I, —CF₃, —CN, —OH, —OCH₃, —OCH₂CH₃, —OCF₃, aC₁˜C₁₂ alkyl or a C₂˜C₁₂ alkenyl.

In addition, the novel compound according to the present invention is avinylsulfone derivative represented by the following Formula 2:

wherein G is

each of W¹ and W² independently represents —H, —CH₃, —CH₂CH₃, —F, —Cl,—Br or —CF₃;

each of X¹ and X² independently represents —O—, —NH—, —CH₂CH₂O—,—CH₂CH₂NH— or —(CH₂)_(m)—, and m is 1 or 2;

each of A¹ and A² independently represents a C₁˜C₁₂ alkylene, a C₂˜C₁₂alkenylene, —(CH₂CH₂O)_(n)—, —(CH₂CHCH₃O)_(n)— or —(CHCH₃CH₂O)_(n)—, andn is an integer of 1˜5;

each of Y¹˜Y⁴ independently represents —O—, —NH—, —(CH₂)_(p)—, —CH═CH—,—C≡C—, —C(═O)O—, —OC(═O)— or —C(═O)—, and p is an integer of 0˜2;

each of E¹ and E² independently represents

each of a and b independently represents an integer of 0˜2; and

each of Q¹˜Q⁸, R¹˜R⁴ and R⁶˜R⁹ independently represents —H, —F, —Cl,—Br, —I, —CN, —OH, —CH₃, —CH₂CH₃ or —C(═O)CH₃.

The vinylsulfone derivatives represented by Formula 1 and Formula 2 areliquid crystal compounds applicable to a compensation film for liquidcrystal display device, which improves view angles of various displaydevices.

In the vinylsulfone derivative represented by Formula 1, non-limitingexamples of the C₂˜C₁₂ alkenylene as A¹ include —CH═CH—, —CH═CCH₃—,—CH₂CH═CH—, —CH═CHCH₂CH₂—, —CH₂CH═CHCH₂—, —CH₂CH₂CH═CH—,—CH═CHCH₂CH₂CH₂—, —CH₂CH═CHCH₂CH₂—, —CH₂CH₂CH═CHCH₂—, —CH₂CH₂CH₂CH═CH—,or the like. Additionally, non-limiting examples of the C₂˜C₁₂ alkenylas R⁵ include —CH═CH₂, —CH═CHCH₃, —CH₂CH═CH₂, —CH═CHCH₂CH₃,—CH₂CH═CHCH₃, —CH₂CH₂CH═CH₂, —CH═CHCH₂CH₂CH₃, —CH₂CH═CHCH₂CH₃,—CH₂CH₂CH═CHCH₃, —CH₂CH₂CH₂CH═CH₂, or the like.

In the vinylsulfone derivative represented by Formula 2, the C₂˜C₁₂alkenylene groups as A¹ and A² are independent from each other, andnon-limiting examples of the C₂˜C₁₂ alkenylene include —CH═CH—,—CH═CCH₃—, —CH₂CH═CH—, —CH═CHCH₂CH₂—, —CH₂CH═CHCH₂—, —CH₂CH₂CH═CH—,—CH═CHCH₂CH₂CH₂—, —CH₂CH═CHCH₂CH₂—, —CH₂CH₂CH═CHCH₂—, —CH₂CH₂CH₂CH═CH—,or the like.

In one preferred embodiment of the vinylsulfone derivative representedby Formula 1, Y¹ may be —O—, Y² may be —C(═O)O—, ring B and ring C maybe aromatic rings, and Q¹˜Q⁴ may be H. Such a vinylsulfone derivativemay be represented by the following Formula 3:

wherein X¹, A¹, E¹, a and R¹˜R⁵ are the same as defined in the aboveFormula 1.

In one preferred embodiment of the vinylsulfone derivative representedby Formula 2, each of Y¹ and Y⁴ may be —O—, Y² may be —C(═O)O—, Y³ maybe —OC(═O)—, ring B, ring C and ring D may be aromatic rings, each ofQ¹˜Q⁸ may be H, and each of a and b may be 0. Such a vinylsulfonederivative may be represented by the following Formula 4:

wherein G, X¹, X², A¹, A², R¹, R², R³ and R⁴ are the same as defined inthe above Formula 2.

In another preferred embodiment of the vinylsulfone derivativerepresented by Formula 1, A¹ may be a C₁˜C₁₂ alkylene, Y¹ may be —O—, Y²may be —C(═O)O—, ring B and ring C may be aromatic rings, and each ofQ¹˜Q⁴ may be H. Such a vinylsulfone derivative may be represented by thefollowing Formula 5:

wherein n is an integer of 1˜12; and X¹, E¹, a and R¹˜R⁵ are the same asdefined in the above Formula 1.

In another preferred embodiment of the vinylsulfone derivativerepresented by Formula 2, G may be vinylsulfone, each of A¹ and A² maybe a C₁˜C₁₂ alkylene, each of Y¹ and Y⁴ may be —O—, Y² may be —C(═O)O—,Y³ may be —OC(═O)—, ring B, ring C and ring D may be aromatic rings,each of Q¹˜Q⁸ may be H, and each of a and b may be 0. Such avinylsulfone derivative may be represented by the following Formula 6:

wherein each of n₁ and n₂ independently represents an integer of 1˜12;and X¹, X², R¹, R², R³ and R⁴ are the same as defined in the aboveFormula 2.

In still another preferred embodiment of the vinylsulfone derivativerepresented by Formula 2, G may be acryl, each of A¹ and A² may be aC₁˜C₁₂ alkylene, each of Y¹ and Y⁴ may be —O—, Y² may be —C(═O)O—, Y³may be —OC(═O)—, ring B, ring C and ring D may be aromatic rings, eachof Q¹˜Q⁸ may be H, and each of a and b may be 0. Such a vinylsulfonederivative may be represented by the following Formula 7:

wherein each of n₁ and n₂ independently represents an integer of 1˜12;and W¹, X¹, X², R¹, R², R³ and R⁴ are the same as defined in the aboveFormula 2.

In yet another preferred embodiment of the vinylsulfone derivativerepresented by Formula 2, G may be vinylsilane, each of A¹ and A² may bea C₁˜C₁₂ alkylene, each of Y¹ and Y⁴ may be —O—, Y² may be —C(═O)O—, Y³may be —OC(═O)—, ring B, ring C and ring D may be aromatic rings, eachof Q¹˜Q⁸ may be H, and each of a and b may be 0. Such a vinylsulfonederivative may be represented by the following Formula 8:

wherein each of n₁ and n₂ independently represents an integer of 1˜12;and W², X¹, X², R¹, R², R³ and R⁴ are the same as defined in the aboveFormula 2.

Particular examples of the vinylsulfone derivatives represented byFormula 1 and Formula 2 include the following compounds, but the scopeof the present invention is not limited thereto:

According to the present invention, the vinylsulfone derivativerepresented by Formula 1 may have stereoisomers, if A¹ is alkenylene, orring B, ring C and/or E¹ is cyclohexylene. Herein, the vinylsulfonederivative having stereoisomers is preferably present in a trans-formwith liquid crystal characteristics. Additionally, stereoisomers of thevinylsulfone derivative may be present in a ratio oftrans-isomer:cis-isomer of 85:15˜100:0.

Also, the vinylsulfone derivative represented by Formula 2 may havestereoisomers, if A¹ and/or A² is alkenylene, or ring B, ring C, ring D,E¹ and/or E² is cyclohexylene. Herein, the vinylsulfone derivativehaving stereoisomers is preferably present in a trans-form with liquidcrystal characteristics. Additionally, stereoisomers of the vinylsulfonederivative may be present in a ratio of trans-isomer:cis-isomer of85:15˜100:0.

Hereinafter, methods for preparing the vinylsulfone derivative accordingto the present invention will be explained in more detail.

The vinylsulfone derivative according to the present invention,represented by the following Formula 5, may be prepared by way of thefollowing Reaction Scheme 1:

wherein X¹, E¹, a, R¹, R², R³, R⁴ and R⁵ are the same as defined in theabove Formula 1, and n is an integer of 1˜12.

In the case of a compound represented by Formula 10 wherein R⁵ is —OH,it is possible to obtain a compound having vinylsulfone groups attachedto both ends thereof as well as a mono-vinylsulfone derivativerepresented by Formula 5.

Additionally, the vinylsulfone derivative according to the presentinvention, represented by the following Formula 6, may be prepared byway of the following Reaction Scheme 2:

wherein X¹, R¹, R², R³ and R⁴ are the same as defined in the aboveFormula 2, and n is an integer of 1˜12.

In Reaction Schemes 1 and 2, there is no particular limitation in thecoupling reagent. Non-limiting examples of the coupling reagent includeEDC or DCC. Also, the coupling reaction of an acid with an alcohol maybe performed by using thionyl chloride or oxalyl chloride in thepresence of an alcohol solvent.

Herein, the compound of Formula 9 used in the above Reaction Schemes 1and 2 may be prepared by way of the following Reaction Scheme 3:

wherein n is an integer of 1˜12, and X¹ is the same as defined in theabove Formula 1.

The linker used in Reaction Scheme 3 may also include alkylene oxidesand alkenyl alcohols, besides alkyl alcohols represented by the formulaof HO—(CH₂)_(n)-Q, and vinylsulfone derivatives obtained by using suchalkylene oxides and alkenyl alcohols are also included in the scope ofthe present invention. Additionally, there is no particular limitationin the base used in Reaction Scheme 3, and conventional base compoundsknown to those skilled in the art may be used.

Further, the vinylsulfone derivative according to the present invention,represented by the following Formula 14, may be prepared by way of thefollowing Reaction Scheme 4:

wherein E¹, a, R¹, R², R³, R⁴ and R⁵ are the same as defined in theabove Formula 1, n is an integer of 1˜12, and X³ is —O— or —CH₂CH₂O—.

Herein, the compound represented by Formula 13 may be prepared by way ofthe following Reaction Scheme 5:

wherein E¹, a, R¹, R², R³, R⁴ and R⁵ are the same as defined in theabove Formula 1, and n is an integer of 1˜12.

In Reaction Scheme 5, the compound represented by Formula 15 may beprepared from 4-hydroxybenzoic acid and the compound represented byFormula 10 via Dean-Stark reaction, or in the presence of thionylchloride or oxalyl chloride, but is not limited thereto. The linker usedto prepare the compound of Formula 13 from the compound of Formula 15may also include alkylene oxides and alkenyl alcohols, besides alkylalcohols represented by the formula of HO—(CH₂)_(n)-Q, and vinylsulfonederivatives obtained by using such alkylene oxides and alkenyl alcoholsare also included in the scope of the present invention. Additionally,there is no particular limitation in the base used in Reaction Schemes 4and 5, and conventional base compounds known to those skilled in the artmay be used.

Further, the vinylsulfone derivative according to the present invention,represented by the following Formula 17, may be prepared by way of thefollowing Reaction Scheme 6:

wherein R¹, R², R³ and R⁴ are the same as defined in the above Formula2, n is an integer of 1˜12, and X³ is —O— or —CH₂CH₂O—.

Herein, the compound of Formula 16 may be prepared by way of thefollowing Reaction Scheme 7:

wherein R¹, R², R³ and R⁴ are the same as defined in the above Formula2, and n is an integer of 1˜12.

In Reaction Scheme 7, the compound of Formula 19 may be prepared in thesame manner as the preparation of the compound represented by Formula 15in Reaction Scheme 5, but is not limited thereto. Additionally, there isno particular limitation in the base used in Reaction Schemes 6 and 7,and conventional base compounds known to those skilled in the art may beused.

Further, the vinylsulfone derivative according to the present invention,represented by the following Formula 22, may be prepared by way of thefollowing Reaction Scheme 8:

wherein W¹, X², R¹, R², R³ and R⁴ are the same as defined in the aboveFormula 2, each of n₁ and n₂ independently represents an integer of 1˜2,and X³ is —O— or —CH₂CH₂O—.

Herein, the compound of Formula 20 may be prepared by way of thefollowing Reaction Scheme 9:

wherein R¹, R², R³ and R⁴ are the same as defined in the above Formula1, and n₁ is an integer of 1˜12. Additionally, in the compoundsrepresented by Formula 20, Formula 23 and Formula 24, P represents aprotecting group generally known to those skilled in the art, andnon-limiting examples of the protecting group include THP, TBS, or thelike.

In Reaction Scheme 9, the compound of Formula 24 may be prepared in thesame manner as the preparation of the compound represented by Formula 15in Reaction Scheme 5, but is not limited thereto. Additionally, there isno particular limitation in the base used in Reaction Schemes 8 and 9,and conventional base compounds known to those skilled in the art may beused.

Further, the vinylsulfone derivative according to the present invention,represented by the following Formula 25, may be prepared by way of thefollowing Reaction Scheme 10:

wherein W², X², R¹, R², R³ and R⁴ are the same as defined in the aboveFormula 2, each of n₁ and n₂ is an integer of 1˜12, and X³ is —O— or—CH₂CH₂O—.

Methods for preparing the vinylsulfone derivatives according to thepresent invention also include other methods performed via a reactionpath similar to Reaction Schemes 1˜10.

The vinylsulfone derivative obtained as described above is well mixedwith various liquid crystal materials. Also, the vinylsulfone derivativeis physically and chemically stable and is stable against heat andlight, under the application conditions of conventional liquid crystaldisplay devices, and forms a liquid crystal mesophase at a preferredrange of temperatures.

Accordingly, the present invention also provides a liquid crystalcomposition comprising at least one vinylsulfone derivative selectedfrom the group consisting of the vinylsulfone derivatives represented byFormula 1 and Formula 2.

Each vinylsulfone derivative is used in the liquid crystal compositionin an amount of 0.1˜99.9 wt %, preferably of 1˜180 wt, based on thetotal weight of the composition.

The liquid crystal composition according to the present invention mayfurther comprise other liquid crystal compounds currently used in theconventional liquid crystal composition in addition to the abovevinylsulfone derivative. Such compounds may be used at various ratios asdesired.

Additionally, the liquid crystal composition according to the presentinvention may further comprise suitable additives, if necessary.Non-limiting examples of such additives include a chiral dopant or aleveling agent that inhibits a spiral structure of liquid crystal orreverse distortion of liquid crystal.

The liquid crystal composition according to the present invention may beprepared in a conventional manner. Typically, various components forforming the liquid crystal composition are dissolved at room temperatureor high temperature.

Further, the present invention provides a compensation film for liquidcrystal display device, which comprises the vinylsulfone derivative orthe liquid crystal composition according to the present invention.

Particular examples of the compensation film for liquid crystal displaydevice include A-plate type compensation films, B-plate typecompensation films, (+)C-plate type compensation films, (−)C-plate typecompensation films, or the like.

Reference will now be made in detail to the preferred embodiments of thepresent invention. However, the following examples are illustrativeonly, and the scope of the present invention is not limited thereto.

EXAMPLE 1

First, 4-hydroxybenzoic acid and 4-methoxyphenol were heated at 100° C.for 10 hours in benzene as a solvent at a mole ratio of 1:1 with a smallamount of sulfuric acid added thereto, while removing water. After thecompletion of the reaction, the organic layer was dissolved in ether andwashed with water several times to remove sulfuric acid used to performthe reaction. Next, the organic solvent was dewatered with anhydrousmagnesium sulfate, and the resultant product was subjected todistillation under reduced pressure to obtain a yellow solid, which, inturn, was washed with ether several times to obtain a white estercompound at a yield of about 85%.

The above ester compound was dissolved in butanone as a solvent, 1.2equivalents of K₂CO₃ and 1.1 equivalents of 6-bromo-1-hexanol were addedthereto, and the reaction mixture was stirred thoroughly at about 80° C.for about 20 hours. Next, the salt formed from the reaction was removedby using ether and water, and the reaction product was subjected todistillation under reduced pressure to obtain a solid organic compound,which, in turn, was washed with hexane several times to obtain analcohol compound as a white solid at a yield of 92%.

The above alcohol compound and 1.2 equivalents of chlorovinyl-sulfonewere dissolved into CH₂Cl₂ as a solvent, and 1.1 equivalents of TEA and0.2 equivalents of DMAP were added thereto at low temperature. Thereaction mixture was allowed to react at low temperature for about 1hour and the reaction product was worked up with water. Then, theresultant product was subjected to chromatography using silica gel toobtain the final vinylsulfone derivative (1) at a yield of 75%. ¹HNMR(400 MHz, CDCl₃): δ 1.47˜1.57 (m, 4H), 1.78˜1.88 (m, 4H), 3.83 (s, 3H),4.05 (t, 2H), 4.16 (t, 2H), 6.13 (d, 1H), 6.36 (d, 1H), 6.55 (dd, 1H),6.91˜6.98 (m, 4H), 7.15 (d, 2H), 8.14 (d, 2H).

EXAMPLE 2

First, 4-hydroxybenzoic acid and 2-methylhydroquinone were heated at180° C. for about 4 hours in diethylbenzene as a solvent at a mole ratioof 2:1 with a small amount of TsOH added thereto, while removing water.After the completion of the reaction, the reaction mixture was filteredto obtain a crude solid compound, which, in turn, was washed with waterand with ether several times to obtain an ester compound as a whitesolid at a yield of 85%.

The above diester compound was dissolved in butanone as a solvent, 2.4equivalents of K₂CO₃ and 2.2 equivalents of 6-bromo-1-hexanol were addedthereto, and the reaction mixture was stirred thoroughly at about 80° C.for about 20 hours. The salt formed from the reaction was removed byusing ether and water and the reaction mixture was subjected todistillation under reduced pressure to obtain an organic compound as asolid, which, in turn, was washed with hexane several times to obtain adi-alcohol compound as a white solid at a yield of 80%.

The above di-alcohol compound and 2.2 equivalents of chlorovinyl-sulfonewere dissolved in CH₂Cl₂ as a solvent, and 2.2 equivalents of TEA and0.2 equivalents of DMAP were added thereto at low temperature. Thereaction mixture was allowed to react at low temperature for about 1hour, and then worked up with water. Then, the reaction mixture wassubjected to column chromatography using silica gel to obtain the finalvinylsulfone derivative (2) at a yield of 65%. ¹HNMR (400 MHz, CDC₃): δ1.44˜1.59 (m, 8H), 1.70˜1.80 (m, 8H), 2.25 (s, 3H), 4.05 (t, 4H), 4.15(t, 4H), 6.12 (d, 2H), 6.40 (d, 2H), 6.55 (dd, 2H), 6.95˜7.00 (m, 4H),7.06 (dd, 1H), 7.12 (d, 1H), 7.19 (d, 1H), 8.14˜8.18 (m, 4H).

EXAMPLE 3

The ester compound, obtained from 4-hydroxybenzoic acid and4-methoxyphenol at a mole ratio of 1:1, was dissolved in butanone as asolvent, 1.2 equivalents of K₂CO₃ and 1.1 equivalents of3-bromo-1-propanol were added thereto, and the reaction mixture wasstirred thoroughly at about 80° C. for about 10 hours. The salt formedfrom the reaction was removed by using ether and water, and the reactionmixture was subjected to distillation under reduced pressure to obtainan organic compound as a solid, which, in turn, was washed with hexaneseveral times to obtain a white solid at a yield of 95%.

The white solid compound and 1.2 equivalents of divinyl-sulfone weredissolved in CH₂Cl₂ as a solvent, 1.1 equivalents of DBU were addedthereto, and the reaction mixture was allowed to react for about 40hours. Then, the reaction mixture was subjected to column chromatographyusing silica gel to obtain the final vinylsulfone derivative (3) at ayield of 81%. ¹HNMR (400 MHz, CDC₃): δ 2.04˜2.21 (m, 2H), 3.26 (t, 2H),3.69 (t, 2H), 3.83 (s, 3H), 3.90 (t, 2H), 4.15 (t, 2H), 6.03 (d, 1H),6.39 (d, 1H), 6.69 (dd, 1H), 6.91˜6.98 (m, 4H), 7.13 (d, 2H), 8.14 (d,2H).

EXAMPLE 4

First, 4-hydroxybenzoic acid and 2-methylhydroquinone were heated atabout 180° C. for about 4 hours in diethylbenzene as a solvent at a moleratio of 2:1 with a small amount of TsOH added thereto, while removingwater. After the completion of the reaction, the reaction mixture wasfiltered to obtain a crude compound, which, in turn, was washed withwater and with ether several times to obtain an ester compound as awhite solid at a yield of 85%.

Next, 1.0 equivalent of the above diester compound and 2.2 equivalentsof 3-bromo-1-propanol were dissolved in butanone as a solvent, 2.2equivalents of K₂CO₃ was added thereto, and the reaction mixture wasstirred thoroughly at 80° C. for about 10 hours. The reaction mixturewas worked up with ether and water, and subjected to distillation underreduced pressure to remove the organic solvent. The solid compoundobtained from the preceding step was washed with hexane to obtain awhite di-alcohol compound at a yield of 90%.

Then, 1.0 equivalent of the above di-alcohol compound was dissolved inCH₂Cl₂ as a solvent, and 2.2 equivalents of divinyl-sulfone and theequivalent amount of DBU were added thereto. The reaction mixture wasallowed to react at room temperature for about 40 hours. After that, thereaction mixture was subjected to column chromatography using silica gelto obtain the final compound (4) as a pale yellow solid at a yield of70%. ¹HNMR (400 MHz, CDCl₃): δ 2.09˜2.22 (m, 4H), 2.24 (s, 3H), 3.27 (t,4H), 3.71 (t, 4H), 3.92 (t, 4H), 4.15 (t, 2H), 6.05 (d, 2H), 6.39 (d,2H), 6.70 (dd, 2H), 6.97˜7.01 (m, 4H), 7.06 (dd, 1H), 7.13 (d, 1H), 7.19(d, 1H), 8.14˜8.18 (m, 4H).

EXAMPLE 5

First, 1.2 equivalents of divinylsulfone and 3-bromo-1-propanol weredissolved in CH₂Cl₂, 1.1 equivalents of DBU was added thereto, and thereaction mixture was allowed to react at room temperature for about 20hours. Next, the reaction mixture was separated by using silica gel.

Then, 1 equivalent of the compound and 1 equivalent of 4-hydroxybenzoicacid were added to a mixed solvent containing THF:H₂O (1:1), 1.1equivalents of KOH was added thereto, and the reaction mixture washeated for about 10 hours. The solid obtained from the reaction wasfiltered off, and washed with water and ether to obtain an acid as apale yellow solid at a yield of 75%.

After that, 1.0 equivalent of the above acid compound, 1.0 equivalent of4-cyanophenol and 1.2 equivalents of EDC were dissolved in CH₂Cl₂, andthe reaction mixture was allowed to react at room temperature for about10 hours. After the completion of the reaction, the reaction mixture wasseparated by using silica gel to obtain the final vinylsulfonederivative (5) at a yield of 85%. ¹HNMR (400 MHz, CDCl₃): δ 2.05˜2.19(m, 2H), 3.25 (t, 2H), 3.68 (t, 2H), 3.91 (t, 2H), 4.18 (t, 2H), 6.05(d, 1H), 6.38 (d, 1H), 6.68 (dd, 1H), 6.99 (d, 2H), 7.33 (d, 2H), 7.75(d, 2H), 8.13 (d, 2H).

EXAMPLE 6

The final vinylsulfone derivative (6) was obtained at a yield of 78% byusing EDC in the same manner as described in Example 5. ¹HNMR (400 MHz,CDCl₃) δ 0.91 (t, 3H), 0.94˜1.11 (m, 2H), 1.18˜1.47 (m, 6H), 1.84˜1.88(m, 4H), 2.04˜2.19 (m, 2H), 2.41 (t, 1H), 3.25 (t, 2H), 3.69 (t, 2H),3.90 (t, 2H), 4.15 (t, 2H), 6.03 (d, 1H), 6.40 (d, 1H), 6.69 (dd, 1H),6.96 (d, 2H), 7.11 (d, 2H), 7.25 (d, 2H), 8.14 (d, 2H).

EXAMPLE 7 Liquid Crystal Composition 1

Liquid Crystal Composition 1 was prepared by using the followingcomponents:

EXAMPLE 8 Liquid Crystal Composition 2

Liquid Crystal Composition 2 was prepared by using the followingcomponents:

EXAMPLE 9 Liquid Crystal Composition 3

Liquid Crystal Composition 3 was prepared by using the followingcomponents:

EXAMPLE 10 Manufacture of +C Type Compensation Film

First, 9.289 of the liquid crystal composition 1 according to Example 7was dissolved in 15 g of toluene and 15 g of xylene. Then, 600 mg ofIrgacure 907, 40 mg of FC-4430 and 80 mg of BYK-300 were added theretoand the reaction mixture was shaken sufficiently. After completelydissolving the materials, particles were removed by using a particlefilter. The resultant solution was bar-coated onto an oriented COP(cycloolefin polymer) having a thickness of 80 μm and treated with analigning layer by using a wire bar. The coated product was dried in anoven at 50° C. for 1 minute, and UV rays (200˜80 W/m) were irradiatedthereto to provide a +C type compensation film.

EXAMPLE 11 Manufacture of +C Type Compensation Film

A +C type compensation film was manufactured in the same manner asdescribed in Example 10, except that Liquid Crystal Composition 2according to Example 8 was used instead of Liquid Crystal Composition 1according to Example 7.

EXAMPLE 12 Manufacture of +C Type Compensation Film

A +C type compensation film was manufactured in the same manner asdescribed in Example 10, except that Liquid Crystal Composition 3according to Example 9 was used instead of Liquid Crystal Composition 1according to Example 7.

COMPARATIVE EXAMPLE 1 Manufacture of +C Type Compensation Film

A +C type compensation film was manufactured in the same manner asdescribed in Example 10, except that Merck RM257 was used instead ofLiquid Crystal Composition 1 according to Example 7. After drying thecoating layer, a dewetting phenomenon occurred. Also, a white turbidnon-uniform film was formed after curing.

[Determination of Physical Properties of Compensation Films]

Each of the +C type compensation films according to Examples 10˜12 wasdetermined for its thickness and refraction index.

More particularly, the film coatability was evaluated by using apolarizing microscope and the film thickness was measured by using amicro-gauge. Also, the birefringence index was measured at an wavelengthof 550 nm by using an Abbe refractometer. The results are shown in thefollowing Table 1. TABLE 1 In-plane Out-of-plane BirefringenceCompensation Thickness refraction refraction index Film (um) index(n_(xy)) index (n_(z)) (Δn) Ex. 10 1 1.492 1.621 0.129 Ex. 11 1 1.4811.623 0.142 Ex. 12 1 1.485 1.644 0.159

As can be seen from Table 1, the compensation films obtained by usingthe liquid crystal composition comprising the vinylsulfone derivativeaccording to the present invention have excellent film coatability,allow the formation of a transparent film after curing, and show uniformfilm appearance with a birefringence index (Δn) of 0.129˜0.159.

INDUSTRIAL APPLICABILITY

As can be seen from the foregoing, the novel vinylsulfone derivativeaccording to the present invention and the liquid crystal compositioncomprising the same have high refractive anisotropy characteristics.Additionally, a high-quality view angle compensation film, whichimproves a contrast ratio measured at a tilt angle when compared to acontrast ratio measured from the front surface and minimizes colorvariations in a black state depending on view angles, can be fabricatedby using the liquid crystal composition according to the presentinvention.

While this invention has been described in connection with what ispresently considered to be the most practical and preferred embodiment,it is to be understood that the invention is not limited to thedisclosed embodiment and the drawings. On the contrary, it is intendedto cover various modifications and variations within the spirit andscope of the appended claims.

1. A vinylsulfone derivative represented by the following Formula 1:

wherein X¹ is —O—, —NH—, —CH₂CH₂O—, —CH₂CH₂NH— or —(CH₂)_(m)—, and m is1 or 2; A¹ is a C₁˜C₁₂ alkylene, a C₂˜C₁₂ alkenylene, —(CH₂CH₂O)_(n)—,—(CH₂CHCH₃O)— or —(CHCH₃CH₂O)_(n)—, and n is an integer of 1˜5; each ofY¹ and Y² independently represents —O—, —NH—(CH₂)_(p)—, —CH═CH—, —C≡C—,—C(═O)O—, —OC(═O)— or —C(═O)—, and p is an integer of 0˜2;

a is an integer of 0˜2; each of Q¹˜Q⁴, R¹˜R⁴ and R⁶˜R⁹ independentlyrepresents —H, —F, —Cl, —Br, —I, —CN, —OH, —CH₃, —CH₂CH₃ or —C(═O)CH₃;and R⁵ is —H, —F, —Cl, —Br, —I, —CF₃, —CN, —OH, —OCH₃, —OCH₂CH₃, —OCF₃,a C₂˜C₁₂ alkyl or a C₂˜C₁₂ alkenyl.
 2. A vinylsulfone derivativerepresented by the following Formula 2:

wherein G is

each of W¹ and W² independently represents —H, —CH₃, —CH₂CH₃, —F, —Cl,—Br or —CF₃; each of X¹ and X² independently represents —O—, —NH—,—CH₂CH₂O—, —CH₂CH₂NH— or —(CH₂)_(m)—, and m is 1 or 2; each of A¹ and A²independently represents a C₁˜C₁₂ alkylene, a C₂˜C₁₂ alkenylene,—(CH₂CH₂O)_(n)—, —(CH₂CHCH₃O)_(n)— or —(CHCH₃CH₂O)_(n)—, and n is aninteger of 1˜5; each of Y¹˜Y⁴ independently represents —O—, —NH—,—(CH₂)_(p)—, —CH═CH—, —C≡C—, —C(═O)O—, —OC(═O)— or —C(═O)—, and p is aninteger of 0˜2;

each of E¹ and E² independently represents

each of a and b independently represents an integer of 0˜2; and each ofQ¹˜Q⁸, R¹˜R⁴ and R⁶˜R⁹ independently represents —H, —F, —Cl, —Br, —I,—CN, —OH, —CH₃, —CH₂CH₃ or —C(═O)CH₃.
 3. The vinylsulfone derivativeaccording to claim 1, wherein the C₂˜C₁₂ alkenylene as A¹ is —CH═CH—,—CH═CCH₃—, —CH₂CH═CH—, —CH═CHCH₂CH₂—, —CH₂CH═CHCH₂—, —CH₂CH₂CH═CH—,—CH═CHCH₂CH₂CH₂—, —CH₂CH═CHCH₂CH₂—, —CH₂CH₂CH═CHCH₂—, or—CH₂CH₂CH₂CH═CH—; and the C₂˜C₁₂ alkenyl as R⁵ is —CH═CH₂, —CH═CHCH₃,—CH₂CH═CH₂, —CH═CHCH₂CH₃, —CH₂CH═CHCH₃, —CH₂CH₂CH═CH₂, —CH═CHCH₂CH₂CH₃,—CH₂CH═CHCH₂CH₃, —CH₂CH₂CH═CHCH₃, or —CH₂CH₂CH₂CH═CH₂.
 4. Thevinylsulfone derivative according to claim 2, wherein each of the C₂˜C₁₂alkenylene groups as A¹ and A² independently represents —CH═CH—,—CH═CCH₃—, —CH₂CH═CH—, —CH═CHCH₂CH₂—, —CH₂CH═CHCH₂—, —CH₂CH₂CH═CH—,CH═CHCH₂CH₂CH₂—, —CH₂CH═CHCH₂CH₂—, —CH₂CH₂CH═CHCH₂—, or—CH₂CH₂CH₂CH═CH—.
 5. The vinylsulfone derivative according to claim 1,which has stereoisomers and the stereoisomers are present in a ratio of[trans isomer:cis isomer] of 85:15˜100:0.
 6. The vinylsulfone derivativeaccording to claim 2, which has stereoisomers and the stereoisomers arepresent in a ratio of [trans isomer:cis isomer] of 85:15˜100:0.
 7. Thevinylsulfone derivative according to claim 1, which is prepared by wayof the following Reaction Scheme 1:

wherein X¹ E¹, a R¹, R², R³, R⁴ and R⁵ are the same as defined in claim1, and n is an integer of 1˜12.
 8. The vinylsulfone derivative accordingto claim 7, wherein a compound represented by the following Formula 9 isprepared by way of the following Reaction Scheme 3:

wherein n is an integer of 1˜12, and X¹ is the same as defined inclaim
 1. 9. The vinylsulfone derivative according to claim 1, which isprepared by way of the following Reaction Scheme 4:

wherein E¹, a, R¹, R², R³, R⁴ and R⁵ are the same as defined in claim 1,n is an integer of 1˜2, and X³ is —O— or —CH₂CH₂O—.
 10. The vinylsulfonederivative according to claim 2, which is prepared by way of thefollowing Reaction Scheme 2:

wherein X¹, R¹, R², R³ and R⁴ are the same as defined in claim 2, and nis an integer of 1˜12.
 11. The vinylsulfone derivative according toclaim 10, wherein a compound represented by the following Formula 9 isprepared by way of the following Reaction Scheme 3:

wherein n is an integer of 1˜12, and X¹ is the same as defined in claim2.
 12. The vinylsulfone derivative according to claim 2, which isprepared by way of the following Reaction Scheme 6:

wherein R¹, R², R³ and R⁴ are the same as defined in claim 2, n is aninteger of 1˜12, and X³ is —O— or —CH₂CH₂O—.
 13. The vinylsulfonederivative according to claim 2, which is prepared by way of thefollowing Reaction Scheme 8:

wherein W¹, X², R¹, R², R³ and R⁴ are the same as defined in claim 2,each of n₁ and n₂ independently represents an integer of 1˜12, X³ is —O—or —CH₂CH₂O—, and P is a protecting group.
 14. The vinylsulfonederivative according to claim 2, which is prepared by way of thefollowing Reaction Scheme 10:

wherein W², X², R¹, R², R³ and R⁴ are the same as defined in claim 2,each of n₁ and n₂ is an integer of 1˜12, and X³ is —O— or —CH₂CH₂C—. 15.A liquid crystal composition comprising at least one vinylsulfonederivative selected from the group consisting of the vinylsulfonederivative represented by the following Formula 1 and the vinylsulfonederivative represented by the following Formula 2:

wherein X¹, A¹, Y¹, Y², ring B, ring C, E¹, a and R⁵ are the same asdefined in claim 1; and

wherein G, X¹, X², A¹, A², Y¹, Y², Y³, Y⁴, ring B, ring C, ring D, E¹,E², a and b are the same as defined in claim
 2. 16. The liquid crystalcomposition according to claim 15, wherein each vinylsulfone derivativecontained in the liquid crystal composition is used in an amount of 1˜80wt % based on the total weight of the composition.
 17. A compensationfilm for liquid crystal display device, which comprises the liquidcrystal composition as defined in claim
 15. 18. The compensation filmfor liquid crystal display device according to claim 17, wherein eachvinylsulfone derivative contained in the liquid crystal composition isused in an amount of 1˜80 wt % based on the total weight of thecomposition.
 19. The compensation film for liquid crystal display deviceaccording to claim 17, which is an A-plate type compensation film, aB-plate type compensation film, a (+)C-plate type compensation film, ora (−)C-plate type compensation film.